Process for breaking petroleum emulsions employing certain oxyalkylated amine-modified thermoplastic phenolaldehyde resins



United States Fatenat Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application March 25, 1954 Serial No. 418,787

Claims. (Cl. 252344) The present invention is a continuation-in-part of my co-pending application, Serial No. 398,633, filed December 16, 1953, now abandoned.

This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the invention.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft Waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Attention is directed to my co-pending application, Serial No. 398,633, filed December 16, 1953, which relates to a process for breaking petroleum emulsions employing a demulsifier including products obtained by condensing certain phenol aldheyde resins, therein described in detail, with certain basic secondary amines, also therein described in detail, and alpha-gamma-dimethylalpha-methoxymethylglutaraldehyde.

The present invention may be characterized in that it is concerned with a process for breaking petroleum emulsions employing demulsifiers including the above described reaction products of Serial No. 398,633 further oxyalkylated by means of certain monoepoxides, hereinafter described in detail.

The products obtained by oxyalkylation with a monoepoxide such as ethylene oxide, propylene oxide, butylene oxide or the like, can be subjected to further reaction with a product having both a nitrogen group and 1,2- epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and Spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be Xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene-glycol diethylether, or a low molal alco- 1101, or a mixture to dissolve the appropriate product being examined and then mix with the equal Weight of Xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of Xylene in the emulsification test includes such obvious variant.

Reference is made herein 'toU. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this test with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the water-in-oil type is characterized by the fact that a fiftyfifty solution in xylene, or its equivalent, when mixed with one to three volumes of water and shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be divided into five parts;

Part 1 is concerned with phenol-aldehyde resins suit able for condensation;

Part 2 is concerned with suitable secondary amines which can be employed in conjunction with the resins in the condensation procedure;

Part 3 is concerned with the condensation procedure as such;

Part 4 is concerned with reactions involving the intermediates obtained inthe manner described in Part 3, preceding, and certain alpha-beta monoexpoxides having not over 4 carbon atoms;

Part 5 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms as in the case of resins prepared from tetradccylphenol, substantially para-tetra-decylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. patents: Nos. 2,499,365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atoms also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of pre paring resins useful as intermediates for preparing the products of the present application, andreference is made to that patent for such detailed description and to EX- amples la through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoorpara-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

Reference has been made. toan earlier formula which was in essence an over-simplification representing a phenol-formaldehyde resin. Actually, some other aldehyde, such as ocetaldehyde, propionaldehyde, or butyraldehyde, may be used. The resin unit can be exemplified thus:

H OH OH R R 'nR in which R is the divalent radical obtained from the particular aldehyde employed to formthe resin.

As previously stated, the preparation of resins of the kind herein employed as reactants i'swell "known. See U. S. Patent No. 2,499,368, dated -March 7, 1950, to De Groote and Keiser. Resinscan'bemade using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense, or without any catalyst at all. It is preferable that" the resins employed be substantially neutral. 'In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of free base. 'The amount maybe as small as a 200th of a percent and as much as a few tenths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just units, or just 6 units, etc. It is usually a mixture, for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 01*"512.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For-pun pose of convenience suitable resins are characterized in the following table:

TABLE 1 M01. wt

Ex- Position R of resin ample R of R derived n molecule number orn- (based on n+2) Pheny] Para Formal- 3 992. 5

dehyde Tertiary butyl do.- do 3. 882. 5 Secondary buty1 Ortho do 3. 882. 5 Cyclo-hexyl 3. 1, 025. 5 Tertiary amyl 3. 959. 5 Mixed secondary 3. 805. 5

and tertiary amyl.

Propyl Para. d0 3. 805. 5 Tertiary hexy]. 0..- n 3. 1, 036. 5 Octyl do do 3. 1.190. 5 N'Onyl.. .do -.;do .3. 1, 257. 5 Decyl 3;. 1, 544. 5 Dodecyl 3. 1, 498. 5 Tertiary butyl. 3. 945. 5

memo: woken more) m e-music" UIUICHQ'IU! :zv

Tertiary amvl 3. 1,022. 5 Nonyl 3.. 1,330. 5 "Tertiary butyL 3. 1, 071. 5

Tertiary amyl d0 d0 3. 1, 148. 5 ony 3. 1, 456. 5 Tertiary butyL 3. 1, 008. 5

3. 1,085. 5 y 3. 1,393. 5 Tertiary butyl. 4. 996. 6

dehyde Tertiary arnyl .d0. o 4.2 1.083. 4 Nonyl do do 4. 2 1, 430. 6 Tertiary butyL ,do.. do 4. 8 1, 094. 4 Tertiary amyL. 4. 8 1,189. 6 N 1 4. 8 1,. 570. 4 1. 5 604.0 1. 5 646. 0 1. 5 653. 0 1.5 688. 0 hyde 32a Octyl d0 do 1.5 786.0 d 1. 5 835. 0 2. 0 986. 0

2.0 692. 0 39a Hen o 2.0 748.0 40a Oyclo-hexyl do do 2. 0 740.0

PART 2 As noted previously, a variety of secondary amines free from a primary amino group may be employed. These amines fall into five catgeories, as indicated previously;

One category consists of strongly basic secondary monoamines free from hydroxyl groups whose composition maybe indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicaland may be heterocyclic in a few instances as inthecaseofpiperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a'heterocyclic amine is, of course,

morpholine.

' nonylamine.

ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alpha-methylbenzyiamine, or benzylamine itself, to product; a suitable reactant. Needless to say,

Other somewhat similar secondary amines are those of the composition RO(CH2): as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to I ones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoXy-alpha methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by The secondary category represents secondary amines which are hydroxylated monoamines. These may be illustrated by diethanolamine, methylethanolarnine, dipropanolamine, dibutanolamine and ethylpropanolamine. Suitable primary amines which can be so converted into secondary amines include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc.

Other suitable amines include Z-amino-l-butanol, 2- amino-Z-methyl-l-propanol, 2-amino-2 methyl,1,3 propanediol, Z-amino-Z-ethyl-1,3-propanediol, and tris-(hydroxylmethyDaminoethane. Another example of such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Other suitable compounds are the following:

(CzHsO 021140 C2H4) HOC2H4 ((3311 CzH4O CzH4O C2H4) HO (12H;

(C4Hn0 CH2CH(CH3) 0 (CH5) CHCHE) NH HOClzHa (CH:O CHQCHaO CHzCHsO CHzCHg) HO C2114 (C1130 CHQCHECHECHQCHQCHB) H O C H or comparable compounds having two hydroxylated 7 groups of different lengths as in (HOCHQCHlOCHiCHSOCHQCHZ) Other examples of suitable amines include alpha-methylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; beta-ethylhexylbutanolamine, diglycerylamine, etc. Another type of amine which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactamine and fructamine, such as N hydroxyethylglucamine, N hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Polyamines free from a hydroxyl group may be illustrated by the following:

CaHa

The fourth category consists of polyamines having hydroxylated groups which may be characterized by the following:

CH|\ CH: N C iHdN (hHtN HO CH C nHtOH I (HOCIHOQNOS IgCI O (CSHGOH)R canon H CzHt HOCgHr CaHs o'lmon H NpropyleneN propyleneN HOCQHL CZHzOII HO 02H; CaHcOH Suitable cyclic amidines which may or may not have a hydroxyl group but are free from primary amino groups may be illustrated by the following;

A compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory v, reactant for the herein described condensation procedure.

This can be illustrated in the following manner by a compound such as 2-heptadecyl,l-aminoethylimidazoline which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of Z-heptadccyLlaminoethylimidazoline, which can be illustrated by the following formula:

Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, 2- heptadecyl,l-aminoethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reactedwith-cthyleneimine the net result is to convert a primary amino radical into a secondaryamino radical and also introduces a new primary amine group. If ethylene imine is employed, the not result .is simply to convert 2-heptadecyl;1-aminoethylimid azoline into '2-heptadecyl,l-diethylenediamineoimidazoline. However, if propylene imine is used the net result is a compound which can 'be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., one having both ethylene groups and a propylene group between nitrogen atoms.

PART3 The products obtained by the herein described processes represent cogeneric mixtures'which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula,

although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

The herein described amine-modified resins are obtained from alphagammadimethyl-alpha-,methoxymethylglutaraldehyde and not formaldehyde. Generally speaking, the objective in the preparation of these aminemodified resins is to obtain a heat-convertible compound even by using formaldehyde. It is not necessary to point out the complications involved when alpha-gamma-dimethyl alpha methoxymethylglutaraldehyde is used. See,-for example, U. S. Patent No. 2,031,557 to Bruson. Since the condensation products obtained are not heatconvertible and since temperature up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps, no description is necessary over and above what has been previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these c'ogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt-to be a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in 'fact, usually it is apt to be a solid at distinctly higher temperature, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene or a comparable petro1eum hydrocarbon or a mixture .of such or similarsolvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as noted, and it is not necessary to have a single phase system for reaction.

Alpha gamma dimethyl-alpha-methoxymethylglutaraldehyde is available as the anhydrous material. In fact, it polymerizes on standing in presence of water. I have found no difliculty in promoting the condensation reaction although at times it is desirable to add some solvent having a common solvent elfect. Thus an oxygenated solvent may or may not be employed. Such solvent may be employed in combination with a hydrocarbon solvent such as xylene. However, if the reaction mass is going to be subjected to some further reaction where the solvent may beobjectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the condensation products obtained are invariably dark and particularly reddish or dark red in color.

By and large, the melting point of the condensate is apt to be higher than of comparable condensates obtained by the use of formaldehyde or furfural. As has been suggested previously, this apparently is due to the difunctional property of alpha-gamma-dirnethyl-alphamethoxymethylglutaraldehyde. Indeed, depending on the resin selected and the amine selected the condensate product or reaction mass on a solvent-free basis is apt to be harder than the original resin itself. This is particularly true when all the amino hydrogen atoms present in the amine have entered into reaction.

The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend '10 in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent using a temperature of not over 150 C. and employing vacuum if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been mentioned previously (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this (c) is an effort to be made to purify the reaction mass by'the usual procedure as, for example, a water-wash to remove any unreacted low molal soluble amine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

I have found no advantage in using a low temperature, approximately room temperature, at the start of the reaction although this is sometimes done purely as a matter of convenience. Indeed, using alpha-gamma-dimethyl-alphamethoxymethylglutaraldehyde I have usually done nothing more than prepare the reaction mixture, add a suitable amount of xylene, and reflux for approximately 3 to 6 /2 hours at temperatures varying as the case may be, from 135 to 160 C. Where the amine has a comparatively low basicity I have sometimes added a small amount or approximately 1% of sodium methylate.

However, using a xylene-benzene mixture, for instance, approximately 170 parts of benzene and 35 parts of xylene and a phase-separating trap to eliminate water, I

TABLE II Alpha gamma Solvent dimethyl (xylene Max Resin Amt, alpha unless Time temp. Ex. No. amt., Secondary amine grams methotherwise period, during grams oxy noted), hrs. reaction,

methyl grams C.

lutaraldehyde, grams 175 Di-lsopropanolamine 61 52 172 6. 5 146 150 D1-n-butylarnine 65 43 163 6. 0 158 150 Dl-ethylamine 37 43 154 5. 5 142 150 Dncyclohexylamiue. 91 43 15B 6. 5 162 300 Mprpholine 87 86 300 7. 0 147 300 D i-2-ethylhexylamlne 241 86 293 5. 0 165 225 Bis-(l,3-d1methylbutylam1ne). 139 65 238 225 Di-lsopropanolamine r 100 65 227 4. 0 162 225 Alpha-methy enzylethanolarnine. 124 65 238 3. 5 156 225 Di-ethanolarnine 79 65 225 2. 5 159 225 Aminnethyl ethanolamine- 78 65 233 2. 5 143 225 Diethanolamine 79 65 "-170 2. 5 102 do 79 "55-170 3.0 131. 5 "55-170 3. 5 101 174 115 240 2.0 128 61 52 228 6. 5 144 65 .43 195 5. 5 156 37 43 206 6.0 143 91 43 188 6. 5 162 97 86 389 7.0 ylhexyl) 241 86 396 5. 5 166 N-methy1aml1ne 54 43 107 4. 5 168 Di- (beta-phenylethyl) amin 169 65 303 4. 0 158 295 Di-1s0propanolamine- 100 65 195 3. 5 153 225 Di ethanolamineufl 79 65 300 2. 75 157 188 Di-isopropylamlne. 61 52 225 7. 5 142 188 Di-n-butylamine 65 43 181 6. 0 188 Dl-ethylamine- 37 43 177 5. 5 142 374 Di-cyclohexylamine. 91 43 199 6. 5 160 374 Morpholine 87 86 375 7. 0 156 188 DI-(Z-ethylhexyDamme 241 86 375 5. 0 166 280 N-methylaniline 54 43 193 4. 5 172 280 Dl- (beta-phenylethyl)amine 169 65 293 5. 0 160 280 Dl-isopropanolamlne 100 65 275 3. 5 15B 280 Di-ethanolamine 79 65 273 3.0 160 [1 have found thatI could employ temperatutesbetween 90' and 100 C., and eliminatev the water of condensation by refluxing at this temperature. However, I have found no particular advantage in using this low temperature over and above the high temperature previously noted.

Ex mpl 1b The resin employed was the one previously designated as 28a and had a molecular weight of approximately 600. 175v gr ms of this resin were dissolved in slightly more than an equal weight of xylene and 61 grams of di-isopropanolamine added. 52 grams of alpha-gamma-xlimethyl-alpha-rnethoxymethylglutaraldehyde were added and the mixture stirred for about 35 minutes and then the temperature allowed to rise to approximately 140 C. or. slightly higher, where itwas allowed to reflux for 6.50 hours. During this refluxing period a phase-separating trap was used to remove the Waterof formation. At the end of this time the reaction was complete'and the product was obtained in the form of a xylene solution. A small sample was evaporated to eliminate the xylene. The resultant product was a rather hard somewhat tacky material, being reddish black in color.

Similar products were prepared as indicated in Table I1.

Nora-In the above examples no catalyst was added. In some duplications of the above small amounts of catalyst were added up to 1% to 2% oi'either powdered caustic soda or powdered sodium methylate. No advantage was noted in the use of a catalyst-provided the amine was sufficiently basic.

In Examples 12b, 13b and 14b indicated by the double asterisk the solvent was a mixture of 17-0 parts of benzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 14b and 15b where the ratio was 1 to 3.5 to 1.75 in both instances. p

In Examples lb through 15b the resin employed was the one identified as Example 28a. In Examples 16b through b, the resin employed was the one identified as Example 32a, and in Examples 26b through 35b the resin employed was identified as Example 39a.

Returning now to aconsideration of the structure of the condensate it becomes obvious that one could obtain ring compounds. Using the abbreviated formula previously applied, the simplest ring could be shown thus:

is the tetravalent radical obtained by the elimination of the carbonyl oxygen atoms from alpha-gamma-dimethylalpha-methoxymethylglutaraldehyde.

Obviously, one could have rings with a larger number of members in the ring to say nothing of complications involving alkanol radicals, for instance, the elimination of a hydrogen atom from the alkanol hydroxyl group.

dated May 14,1251. ln-thisparticular instanceiherem described a numberof complicated condcnsatesin which 3% moles of diethanolamine, or the like, moles of formaldehyde, and one mole of the .phenobaldehyde resin, are employed. It corresponding condensates are prepared, replacing Bl moles of formaldehyde by 1% moles of alpha-gamma-dimethyl?alpha-methoxymethylglutaraldehyde, a variety of compounds are obtained which have unusual structure but arestill organic solventtsoluble and susceptible to oxyalkylation. Indeed,v another variety of somewhat more complicated materials are obtained by using as the amine reactant di(hydroxyethyl)N,N ethylene diamine having the following-structure;

Ncn'mv rr "onzuon An initial product can be made treating the amine as if it were nothing more than .a hydroxylated monoamine. Subsequently alpha gamma dimethyl alpha methoxymethylglutaraldehyde may be added up to,'for example, the amount originally employed with the production of linear polymers and in some instances cross-linking, It is understood that regardless of what amine is used the final Product sly s, and must b or nic sol entsoluble. The primary objective is to obtain a condensate h h is organic o v -soluble nd no n iu us e resin- Such condensate is particularly valuable for oxya1l yla= tion. The products so obtained find utility in various, arts.

See my co-pending application, Serial No. 383,928, filed b r 2, 953, now Paten N 2,7 2 366, d e May 1957- This p icu r app ati n is. essential y the same as h n n pplica ion e cep h gly xa is used in of a pha-g mma-dimet yhalph -methnic t ylglutaraldehyde. It is well known that this dialdehyde combines with phenols, melamine, urea, and polyamines to form polymers under appropriate conditions and resins including insoluble resins. The reaction in the present instance where alpha-gamma-dimethyl-alpha-methoxymethylglutaraldehyde replaces glyoxal or pyruvic aldehyde are more complicated by virtue of its ability to react not only with amino radicals but with hydroxyl radicals as well. This property has suggested its use as an insolu- Furthermore, the situation becomes even more complia cated if the ratios are changed to correspond to ratios described in my co-pending application, Serial No. 376,240, filed August 24, '1953, now Patent No. 2,792,365

bilizing agent for proteinaceous material such as leather, animal glue, casein and gelatin and hydroxylated materials such as polyvinyl alcohol, polyvinyl partial acetals and cellulose.

In any event, it is obvious that the reactions involved are complicated and all that is required is that the final product be thermoplastic and organic solvent-soluble. Furthermore, it indicates why it is additionally necessary to characterize the invention in terms of the method of manufacture.

PART 4 At the present time there are available a number of alkylene oxides, particular-1y ethylene oxide or propylene oxide and butylene oxide, either as a single isomer or as .a mixture of isomers. Glycide is available, or readily prepared, The same applies to methylglycide.

Oxyallrylation with any of the aforementioned alkylene oxides is comparatively simple in light of present day 0 dg. In fact, ,it is stated briefly in U. S. Patent No. 2,636,038 dated April 21, 1953, to Brandner, in the following language: The compounds are prepared by the addition reaction between alkylene oxides and substituted oxazolines of the group named hereinbefiore. The addition reaction is advantageously carried out at elevated temperature and pressure and in the pres- ,ence of an alkaline catalyst.

agersgaav l3 xiatediFebruary 24, 195 3,toiEefirootezand.Keiser. :See particularly the subject matter whichappears. inscolumn 7 'ofsxsai'd patent.

Propylene oxide and butylene "oxide react somewhat 'moreslowly than ethylene oxide and may: require a some- What higher temperature, somewhat greateragitation, or an increased amount of alkaline catalyst, such as finely powdered sodium hydroxide or sodium 'methylate. If the 'productto be subjected to oxyalkylation is xylenesohlble or soluble in anyone of a number of inert solvents there isnoparticular difficulty involved. The same is true if the product is a liquid at oxyalkylation temper- :atures. If it isnot soluble or'a -liquid,- then insome cases initial oxyalkylation'can be accomplished by means of an alkylene carbonate, such as ethylene carbonate or propylene carbonate which has a solubility effect as well as acting as an oxyalkylation agent. As soon as a suitable product is obtained by the use of a carbonate further reaction can be completed with the oxide. An alternate procedure sometimes employed with insoluble materials is to reduce "the products to an extremely'finely ground powder and oxyalkylate during suspension usingparticularly vigorous agitation.

All these procedures have been described repeatedly-in thel literature' and, as a matter of fact,rsuitableoperational directions are available from any one of several makers of alkylene oxides.

Example 10 -Bue -to their ready availability,-the-bulk of theoxy- :alkylation :derivatives were-prepared from ethylene oxide,

propylene'oxide, butylene oxide, ora mixture of the same.

Generally speaking, the autoclavesor oxyalkylators employed ranged from approximately 2 gallons in size to approximately gallons in size. The-general procedure was tostart with a fairly small sample; for instance, ap- -proximately 2000*grams,'of' the product to be oxyalkylated and '1000 grams of a solvent such as xylene, or a highboi-ling aromaticsolvent,orthe diethylether of ethyleneglycol, or a mixture of these solvents. Powdered caustic soda, orsodium.methylate, were-added -as acatalyst in anamount generally not: over 2%, and more catalyst was added if the amount dropped to /z% or less. Initial oxyalkylation generally started by adding 50% by weight, 100% by weight, 200% by weight, 300% by weight, 500% by weight etc., until at least ten times as much oxide had been added, at least in some examples. Excellent compounds or suitable raw materials have been obtained by adding as much as 50 parts by weight of oxide to one part of the initial reactant. In some instances the same exampleswere repeated and then reacted with one or more oxides; for instance,=in the table which follows there are examples where an oxyethylated product was oxypropylate'd subsequently; or vice versa. Comparative- ,lysmallsamples, for:instance, one to five grams, were taken at-various stages and tested foremulsifiabilitytactor and also for'demulsifyingeffect on 'crudeoil'emulsions. The tabular data do not reflect the slight discrepancy due to sample withdrawal.

More specifically then, pounds (13,000 gramsyof the condensate previously identified as Example 1b, were mixed with 16 pounds of solvent'(being xylene in this series). The mixture wasplaced in a small autoclave together with one pound (450 grams) of finely -powdere'd caustic soda, and stirred,'and the temperature'raised to approximately 115 C. 7.5 pounds of ethylene oxide were added in approximately 15 minutes. The :pressure during the oxyalkylation was about 10 to 15, pounds per square inch. The resultantpro'duce was a fluid: having a dark amber color and viscousin mixture. 'Except for the withdrawal of a few grams' for:examination,' the prod uct was then subjected to further oxyalkylation with another 7.5 pounds of ethylene oxide and without the addition of any more catalyst or any moresolvent.

Note what. is said .imregardto .these examples-and .sub-

sequent a-examples lllnlhe text immediately.-following and in-zthe tables.

A number of additional examples appear in tabular form in the five tables immediately'following, .to wit, Tables III, IV, V, VI and VII. These are self-explanatory, particularly in regard to the-first three tables. The last two require a little more careful examination. .This is due to an effort tocondense the data and not :burden the text wtih an unduly large volume of detail.

Due to the fact that various size quantities are used the ratios sometimesappear in grams or kilograms and sometimes in pounds. Whenpoundsxareused the-designation is included.

In Tables III, IV and'V successivestagespof oxyalkylation are shown. Small samples of a few grams were withdrawn and tested for solubility and also for demulsification elfectiveness. The withdrawal of such small samples was ignored. In some instances the example was repeated and used subsequently for reaction with one or more other oxides. In some instances the product so obtainedin the first stage of oxyalkylation represented-a tcornparatively large quantity and was subdivided perhaps into one-half or even a smaller fraction, and then this smaller fraction only subjected to oxyalkylation with another oxide. v.As previously noted, no further explanation is required in regard to the first three tables.

In the fourth table, Table VI, it is-to.be noted that Example 1 is derived from Example 80. Referring to Example it will be noted this was derived originally from oxyalkylation-susceptible compound Example lb. In Example 180, oxyalkylation-susceptible compound Example 1b had already been treated with ethylene oxide. Thus, in Table VI, althoughthe oxyalkylation-susceptible compound is' properly designated as Example -8cifor-the reason it is now the reactant'subjected'to oxypropylation, the oxyalkylation-susceptible compound as far as reference to weight goes (in this instance 1350 grams, '3 pounds) goes back to the original compoundiExample lb. This is obvious, and is even-more obvious for vthe'reason that it is subsequently emphasized in connection withlhe weight ratio, as explained subsequently.

It will be noted also thatin the fourthtcolumn in .Table VI the oxide used is marked as indicated vand in each instance the oxide employed in .thissecond stageis shown, in two-instances in Table VI being-propylene oxideand in one instance being ethylene oxide.

Bearing in mind what is said in regard to Example If being derived from Example 8c, which in turn was derived from Example 1b plus ethylene oxide, it should be noted that this table does not, as far as the first four columns go, reflect the amount of oxide which was added in the initial or earlierstage. As previously notedythis does not cause confusion and, in fact, permits holding: the data -to a minimum in light of what is said" next.

Referring now to columns seven, eight, nine and-ten which are concerned with. composition at the end, it'will be noted that these data ido-take into consideration the amount of oxide added initially as well as the oxide during the second stage. Thus although this shows the propylene oxide added it also shows. the original ethylene oxide as representing the five-to-one weight ratio :based on the oxyethylation of the first stage. This can be stated perhaps more simply in .the following Way: On initial examination the table shows'that Example 1f Was-derived from Example 80. As to 1 the composition of Example 80 one need only note that in theaseventh column it shows that 24 pounds of propylene oxide were added and the weight ratio to the oxyalkylationesusceptible compoundExample lb was eight-to-one,-but it also shows that the Weight ratio .of the ethylene oxide at the same stage was also eight-to-one. Thus, without even checking back to a prior table it is obvious 'the' initialma- .terial, Example 80, subjecteditma ,secondzoxyalkylation 15 step, consisted of a product in which one part of the oxyalkylation-susceptible compound was combined with 8 pounds by weight of ethylene oxide, prior to oxypropylation.

163 considerable detail in the previous text. Again it is'to be noted that in the tables the ratios of the oxide to the initial product prior to oxyalkylation is shown so there is no question as to the composition of each example a1- All the data in Tables VI and VII are presented in the 5 though considerable data have been presented in what is same way. We find this is the most simple and concise a comparatively condensed and readily understandable tabular presentation that yet has been developed after a form. considerable series of experimentations, and reports in Note what is said in regard to the color of the products table form. This is true even where three oxides were in the tables. For most industrial purposes there is no employed as for instance in Example lg in Table VII. 10 objection to the color. The products can be decolorized Example lg was obtained from Example 5f in Table VI. by conventional procedure, using bleaching earths, filter- Example 5 as indicated, was obtained by an oxypropylaing clays, charcoal, or the like. A trace or small amount tion of Example 17, and Example If, as previously noted, of catalyst, if present, can be removed for most purposes was obtained from Example 80. The preparation of Exby the mere addition of a comparable amount of hydroample 8c from Example 1b has not been discussed in 15 chloric acid or by any other suitable means.

TABLE III Composition before-Amount of 080,1 catalyst anid solvent constant before and after oxyalkyl- Composition at end Operating conditions at on Ex. Weight ratio End product- No. Color and physical OSC Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, EtO, lyst, solvent used, EtO, EtO to PrO to B110 to pres., temp., of re- No. grams grams NaOH, grams grams 1 oxyalkyloxyalkyloxyalkylp. s. i. 0. action,

grams ation ation ation hrs.

suscept. susccpt. suscept. cmpd. cmpd. cmpd.

30. 0# 450 16.0,; 7. 51 0.25 110-115 Dark amber viscous liquid. 30. 0 7. 450 16. 0 15.0 .50 110-115 34 D0. 30. 0 15. 0 450 15. 0 30. 0 1. 0 110-115 Do. 30. 0 30. 0 450 16. 0 45. 0 1. 5 110-115 4 Do. 30. 0 45. 0 450 15. 0 60. 0 2. 0 110-115 1 Do. 15.0 30.0 225 8.0 60.0 4.0 110-115 2 Dark amber very viscous liquid. 7.5 30.0 112.5 4.0 45.0 6.0 110115 1% Amber-greasy. 7. 5 45. 0 112. 5 4.0 60. 0 8.0 110-115 2 Light amber solid. 12. 5 0 250 10.0 12. 5 1.0 110-115 1% Redglish black liq- 111 c 9c 12.5 12.5 250 10.0 25.0 2.0 10-15 110-115 1% Viscous liquid. 11c-.. 10c 12.5 25.0 250 10.0 31.2 2.5 10-15 110-115 Do. 120... 110-.-- 12.5 31.2 250 10.0 37.5 3.0 10-15 110-115 4 Do. 13c 12c 12.5 37.5 250 10.0 40.0 3.2 10-15 110-115 1 Do. 145". 13c.... 12.5 40.0 250 10.0 50.0 4.0 10-15 110-115 1% Very viscous. 15c... 14c 12.5 50.0 250 10.0 56.2 4.5 10-15 -115 1% Heavy to greasy.

1 Oxyalkylation-susceptible compound. In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE IV Composition bef0re-Arnount oi OSC,1 catalyst atrz d solvent constant before and after oxyalkyl- Composition at end Operating conditions 8 1011 Ex. Weight ratio End product-- No. Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, PrO, lyst, solvent used, PrO, EtO to PrO to B110 to pres., temcp, of re- No. grams grams NaOI-I, grams grams oxyalkyloxyalkyloxyalkylp. s. i. action,

grams ation ation ation hrs.

suscept. suscept. suscept cmpd. cmpd. cmp

11.0# 01? 495 12.0%; 44.0# 4.0 10-15 -125 5 Dark amber viscous liquid.

11. 0 44. 0 495 12. 0 55. 0 o. 0 10-15 115-125 3 Do. 5. 5 33. 0 247. 5 0. 0 05. 0 12. 0 10-15 115-125 4% Do. 5. 5 66. 0 247. 5 5. 0 88. 0 16. 0 10-15 115-125 4 Do. 3. 8 52.8 148. 5 5 59. 4 18. 0 10-15 115-125 2 Do. 3. 3 59. 4 148. 5 3. 0 72. 3 22. 0 10-15 115-125 2% Do. 3. 3 72. 5 148. 5 3. 6 82. 5 25. 0 10-15 115-125 2% D0. 3. 3 82. 5 148. 5 3. 6 92. 4 28. 0 10-15 115-125 3% Do.

10.0 0 450 10.0 80.0 8.0 10-15 115-125 5.0 Do. 5. 0 40. 0 225 5. 0 s0. 0 16. 0 10-15 115-125 4. 0 Do. 2. 5 40.0 112.5 2. 5 50. 0 20. 0 10-15 115-125 3 Do. 2. 5 50. 0 112. 5 2. 5 50. 0 24.0 10-15 115-125 3 Do. 2. 5 60. 0 112.5 2. 5 65. 0 26.0 10-15 115-125 2% Do. 2. 5 55. 0 112. 5 2. 5 70. 0 28. 0 10-15 115-125 2% D0. 2. 5 70. 0 112. 5 2. 5 75. 0 30. 0 10-15 115-125 3 Do.

l Oxyalkyl'ation-susceptible compound. In some instances weights change from gram basis to pound basis.

Such change in unit is obvious.

TABLE V Composition beforeAmount of 080, catalyst aiild solvent constant before and after oxyalkyl- Composition at and Operating conditions a on Ex. Weight ratio End product- No. Color and physical 080 l Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, BuO, iyst, solvent used, IBuO, EtO to PrO to BuO to pres, temp., of re- No. grams grams NaOH, grams grams 1 oxyalkyloxyalkyloxyalkylp. s. 1. 0. action,

grams ation ation ation hrs.

suscept. suscept. suscept. cmpd. empd. cmpd.

468 5, 740 -30 130-135 3% Dark amber viscous liquid. 2, 340 468 5, 740 1. 0 25-30 130-135 3% Do. 4, 680 468 5, 740 1. 5 25-30 130-135 2 D0. 7, 020 468 5, 740 2. 0 25-30 130-135 2 D0. 4, 680 234 2, 870 4.0 25-30 130-135 5 D0. 0# 450 10. 5 1.0 25-30 130-135 2% D0. 10. 0 450 10. 5 2. 0 25-30 130-135 2 Do. 20.0 450 10. 5 4. 0 25-30 130-135 4 D0. 40. 0 450 10. 5 6. 5 25-30 130-135 4% D0. 65. 0 450 10. 5 8. 8 25-30 130-135 5 D0. 0# 825 16. 5# 5 25-30 130-135 2 D0. 9. 25 825 16. 5 1. 0 25-30 130-135 2% Do. 18. 825 16. 5 1. 8 25-30 130-135 4 D0. 33. 3 825 16. 5 2. 24 25-30 130-135 3 D0. 20. 75 412. 5 8. 25 6. 2 25-30 130-135 6 D0.

1 Oxyalkylation-susceptible compound. 3 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE VI Composition before-Amount of 080, catalyst apid solvent constant before and after oxyalkyl- Composition at end Operating conditions a on Ex. Weight ratio End product- No. Color and physical 05C 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used. as lyst, solvent used, as EtO to PrO to BuO to pres., temp, of re- No. grams indicated, N aOH, grams indicated, oxyalkyloxyalkyloxyalkylp. s. 1. action,

grams grams grams 2 ation ation ation hrs.

suseept. suscept. suscept. cmpdfl cmpd. cmpdfi 1, 350 0 PrO 135 720 24. O# PrO 8.0 8.0 10-15 125-130 4 Light amber heavy grease. 1, 350 24. 0?, 135 720 36. 0 8.0 12.0 10-15 125-130 1% Viscous liquid. 1, 350 36. 0 135 720 45.0 8.0 15.0 10-15 125-130 3 D0. 1, 350 45.0 135 720 51.0 8.0 17.0 10-15 125-130 2 Do. 1, 350 51.0 135 720 60.0 8.0 20.0 10-15 125-130 2% Do. 4, 950 0 B110 495 5, 400 4, 950 BuO 16.0 -1. 0 10-15 125-130 1% Dark amber viscous liquid. 4, 950 4, 950 495 5. 400 9, 900 16. 0 2. 0 10-15 125-130 1%; D0. 950 9, 900 495 5, 400 10, 800. 0 16.0 2. 2 10-15 125-130 1% D0. 4, 950 10, 890 495 5, 400 14.85 Kg. 16. 0 3.0 10-15 125-130 3. 0 Do. 4, 950 14. 85 Kg 495 5, 400 44. Kg. 16.0 6.0 10-15 125-130 6.0 Do. 5. 0# 0 PrO 250 5. 25 35. 0# PrO 5.0 8.8 10-15 125-130 3.0 Do. 5. 0 25.0 250 5. 25 50.0 10. 0 8. 8 10-15 125-130 3. 0 Do. 5. 0 50.0 250 5. 25 60. 0 12.0 8. 8 10-15 125-130 1% Do. 5. 0 60.0 250 5. 25 70. O 14. 0 8. 8 10-15 125-130 1% Do. 5. 0 70. 0 250 5.25 90 18.0 8. 8 10-15 125-130 2 D0.

1 Oxyalkylation-susceptible compound.

PART 5 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and efiect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 2 herein described.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is:

1. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic secondary amine free from any primary amino radical and having not more than 32 carbon atoms in any group attached to any amino nitrogen radical and reactive towards alpha-gamma-di- TABLE VII Composition beforeAmount of 080, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions a ion EX. Weight ratio End product- No. Color and physical 05C 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 050 1 used, as lyst, solvent used, as EtO to FIG to BuO to pres, temp., of re No. grams indicated, NaOI-I, grams indicated, oxyalkyloxyalkyloxyalkylp. 5.1. 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpdfi cmpdfi cmpdfi 450 BuO 45 240 450 BuO 8. 0 20.0 1.0 10-15 125-130 2 Light amber viscous liquid.

450 900 45 240 l, 350 8.0 20.0 3. 0 10-15 125-130 3% Do.

495 0 EtO 49. 5 540 495 EtO 1.0 16.0 6.0 -15 125-130 1 Dark amber viscous liquid.

495 1, 980 49. 5 540 2, 970 6.0 16.0 6.0 10-15 125-130 3% Very viscous.

495 2, 970 49. 5 540 3, 960 8.0 16.0 6. 0 10-15 125-130 3 Heavy to greasy.

450 0 13120 45.0 472.5 900 2.0 18.0 8.8 10-15 125-130 2 Viscous liquid.

450 900 45.0 472.5 3, 600 8. 0 18.0 8.8 10-15 125-130 5% Very iscous iqu 450 4, 950 45. 0 472. 5 5, 400 12.0 18.0 8.8 10-15 125-130 2% Heavy to greasy.

1 Oxyalkylation-susceptible compound.

methyl alpha methoxymethylglutaraldehyde; and (c) alpha gamma dimethyl alpha methoxymethylglutaraldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and rnethylglycide.

2. The process of claim 1 with the proviso that there be an alkanol radical attached to at least one amino nitrogen atom.

3. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglutaraldehydc; and (0) alpha gamma dimethylalpha methoxymethylglutaraldehyde; said condensation reaction being conducted at a temperature sufiiciently highv to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl aplha methoxyrnethylglutaraldehyde; and (c) alpha gamma dimethyl alpha methoxymethylglutaraldchyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glyoide and methylglycide.

5. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglytaraldehyde; and (c) alpha gamma dimethyl alpha methoxymethylglutaraldehyde; said condensation react-ion being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a alpha gamma dimethyl alpha methoxymethylglutaraldehyde derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the ratio of reactants be approximately 1, 2 and 1 respectively; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

67 The process of breaking petroleum emulsions of the water-in-o-il type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, Water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglutaraldehyde; and (0) alpha gamma dirnethyl alpha methoxyrnethylglutaraldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a alpha gamma dimethylalpha methoxymethylglutaraldehyde derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively, with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

7. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethylanon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglutaraldehyde; and (c) alpha gamma dimethyl alpha methoxymethylglutaraldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a alpha gamma dimethylalpha methoxymethylglutaraldehyde derived substituted methylene bridge connecting the amino nitrogen atom With a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atomsand selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

8. The process of breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglutaraldehyde; and alpha gamma dimethyl alpha methoxymethylglutaraldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a aplha gamma dimethylalpha methoxymethylglutaraldehyde derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

9. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenolformaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoam'ine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglutaraldehyde; and (0) alpha gamma dimethyl alpha methoxymethylglutaraldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a alpha gamma dimethyl alpha methoxymethylglutaraldehyde derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylationsusceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

10. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethyla- Lion-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substi tuted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha gamma dimethyl alpha methoxymethylglutaraldehyde; and (0) alpha gamma dimethyl alpha methoxymethylglutaraldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the H ultimate molecule by virtue of a alpha gamma dim'ethyL alpha methoxymethylglutaraldehyde derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylat-ion-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 25 26 carbon atoms and selected from the class consisting of 2,457,634 Bond et a1 Dec. 28, 1948 ethylene oxide, propylene oxide, butylene oxide, glycide 2,507,910 Keiser et a1 May 16, 1950 and methylglycide. 2,55 8,688 Landa June 26, 1951 2,589,200 Monson Mar. 11, 1952 References Cited in the file of this patent 5 95,337 De Groote v, 30, 1954 UNITED STATES PATENTS 2,454,545 Bock et a1. NOV. 23, 1948 

1. THE PROCESS OF BREAKING EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS, SAID SYNTHETIC HYDROPHILE PRODUCT BEING THE PRODUCTS RESULTING FROM A TWO-STEP MANUFACTURING PROCESS CONSISTING OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXUGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 